N-alkylbenzenesulfonyl-n-alkyl taurates



United States Patent Q N-ALKYLBENZENESULFONYL-N-ALKYL TAURATES James M. Cross, Belvidere, N. J., and Max E. Chiddix,

Easton, Pa., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application September 7, 1951, Serial No. 245,638

6 Claims. (Cl. 260508) The present invention relates to N-alkylbenzene-sulfonyl-N-alkyl or aryl-taurates which are effective surface active agents.

United States Patent No. 1,932,180, granted October 24, 1933, to Fritz Guenther et al. discloses the preparation of surface active agents by condensing inter alia a fatty acid chloride With an N-alkyl taurine. These products are sold under the trade-mark Igepons. Such products have very valuable detergent properties and good wetting power.

However, the wetting power thereof is not optimum, and in this connection reference is made to the availability on the market of the ester products, bis-2-ethylhexyl-sodium sulfo succinate, and the products embraced by United States Patent No. 2,315,375, granted on March 30, 1943, to Paul Nawiasky et al.

These ester-like products are among the most powerful wetting agents known. They suffer, however, from the very grave disadvantage that they are unstable in hot acids or alkalies.

We have now discovered a new class of surface active agents which partake of the detergent properties of the aforesaid Igepons" and certain members at least of which have the wetting power of the aforesaid esters without the objectionable instability of said esters. This class of products may be characterized generally as N- alkylbenzenesulfonyl-N-alkylor aryl taurates, and such products, their manufacture and use as surface active agents constitute the purposes and objects of the present invention.

The new class of compounds contemplated herein may be more precisely characterized by the following formula:

wherein R1 is alkyl such as amyl octyl, heptyl, decyl, dodecyl, dimethylheptyl, octadecyl and the like, or cycloalkyl such as cyclohexyl and the like; and R2 is hydrogen or alkyl such as methyl, ethyl, propyl, butyl, amyl and the like, the sum of the carbon atoms in R1, R2, however, being between 6 and 25; R3 is hydrogen, alkyl, such as methyl, ethyl, isopropyl, n-butyl, isobutyl, amyl, hexyl, heptyl, octyl, nonyl, dodecyl and the like, cyclohexyl or aryl such as phenyl and the like, and M is an alkali metal such as sodium, potassium or the like, an alkaline earth metal such as calcium, strontium or the like, or the radical of ammonia or an amine such as ethylarnine, ethanolamine, cyelohexylamine and the like.

Examples of compounds within such formula which we have found to be eminently satisfactory as surface active agents are sodium N-octyltoluenesulfonyl-N- methyltaurate, sodium N-octyltoluenesulfonyl-N- cyclohexyltaurate, sodium N-dodecyltoluenesulfonyl-N-methyltaurate, sodium N-dodecyltoluenesulfonyl-N-n-butyltaurate, sodium N-diamylbenzenesulfonyl-N-methyltaurate, sodium N-diamylbenzenesulfonyl-N-n-butyltaurate, sodium N-diamylbenzenesulfonyl-N-amyltaurate, sodium N-diamylbenzenesulfonyl-N-n-butyltaurate, sodium N- cyclohexylbenzenesulfonyl-N-methyltaurate, sodium N- octyltoluenesulfonyl-N-phenyltaurate, and the corresponding ammonium or amine salts.

The above compounds are prepared by condensing the desired alkylbenzenesulfonyl chloride with the selected taurine in the presence of an acid binding agent such as caustic soda, pyridine or the like. Condensation 2,694,727 Patented Nov. 16, 1954 ice is generally eifected at a temperature ranging from about 10 to 70 C.

The alkylbenzenesulfonyl chlorides are prepared by bringing the selected alkylbenzene into contact with an excess of chlorosulfonic acid at a low temperature, i. e. from about zero to 10 C., followed by stirring the mixture for several hours at slightly higher temperatures such as 15 to 30 C. The mass is then drowned in ice and Water and worked up for the alkylbenzenesulfonyl chloride.

Alternatively the alkylbenzenesulfonyl chloride may be prepared by treating a selected alkylbenzenesulfonic acid with chlorosulfonic acid or thionyl chloride, or by treating a selected sodium alkylbenzenesulfonate with phosphorous pentachloride or chlorosulfonic acid.

Alkylbenzenes which may be used for preparation of the alkylbenzenesulfonyl chlorides are dodecylbenzene, nonylbenzene, diamylbenzene, diheptylbenzene, dihexyltoluene, octyltoluene, Z-phenyl-dodecane, Z-phenyl-octane, 2-phenyl-4,o-dimethylheptane, octadecyltoluene, cyclohexyltoluene, dicyclohexylbenzene and the like.

Suitable taurines for reaction with the sulfonyl chlorides derived from the aforementioned alkylzenzenes are N-methyl-, N-ethyl-, N-isopropyl-, N-n-butyl, N-iso' butyl-, N-amyl-, N-n-propyl-, N-cyclohexyl-, N-hexyl-, N-heptyl-, N-octyl-, N-nonyl-, N-phenyl-, and N-dodecyltaurine.

Amine bases which may be used as alternates of the alkali metals to convert the products into amine salts are ammonia, ethylamine, ethanolamine, cyclohexylamine, dimethylaniline, butylamine, amylamine, triethanolamine, trimethylamine and the like.

The surface active products hereof have unique properties which vary according to the size and number of the alkyl chains present in such products. To illustrate, the compound derived from docecylbenzenesulfonyl chloride on the one hand and methyltaurine on the other had is a good detergent for cotton, being equal in this respect to the product sold under the trade mark lgepon T (product derived from oleic acid chloride and N- methyltaurine). Its wetting strength is also about equal to that of Igepon T. However, the sulfonamide prepared from diamylbenzenesulfonyl chloride and butyltaurine is a very powerful wetting agent, being of about equal power to the aforementioned esters. It possesses, however, the very important advantage over said esters in that it is stable in hot acid or alkali, whereas the esters are not.

It is also possible to build into the products hereof other important properties such as increased brine solubility and better foam stability by variation in the size and number of the alkyl groups.

The most conspicuous property of our products is their pronounced lowering of the surface tension of aqueous solutions which promotes their use in a large field of the technical arts. The possible application of the products are extremely varied. For instance, they can be used as wetting, frothing, or washing agents in the treating and refining of textiles; for converting liquid or solid substances, which per se are insoluble in water (such as hydrocarbons, higher alcohols, fats, oils, waxes, resins, pitches and pitchy substances), into clear solutions or fine, stable dispersions; for carbonizing; for dyeing in acid baths; for dyeing animal fibers with vat dyestuffs; for dyeing in alkaline, acid or neutral baths; for the pasting of dyestuffs, for fulling, sizing, impregnating and bleaching treatments; as cleansing agents in hard water; for dyeing in padding" (impregnating) liquors; for dyeing with diazo preparations; in tanning and mordanting processes; as an aid to soap in acid baths; for dyeing acetate silk with insoluble dyestuffs; as emulsifying agents; as a resist (reserve) for cotton in acid baths; as an aid in dyeing and printing with aniline black; as an aid in desizing textile materials; for the preparation of azodyestuffs in finely divided form; as a fat decomposition agent for the removal of fats; for the cleansing of vegetable fibers; as an aid to the retting of flax; as an aid to mercerizing lyes; for producing foam in fire extinguishers; as a means for improving the absorptive power of fibrous bodies; as an aid in softening baths for hides and skins; as a disinfectant; as an insecticide; and for sulfonating oils and fats.

In addition these products are valuable emulsifiers for insecticide compositions and agricultural sprays such as DDT, 2,4-D, toxaphene, chlordane, dormant or mineral oil sprays, nicotine sulfate, etc.

These products are valuable for use in the petroleum industry as additives for'fuel oils, hydraulic fluids, lubricating oils, cutting oils, greases, as additives to the water on brine used in oil recovery from oil sands or as emulsion breakers for crude oil.

Other valuable uses are in metal cleaning compositions, industrial dry cleaning compositions, additives for rubber latices, foam inhibitors for synthetic rubber latex emulsions, froth flotation agents, additives for road building materials such as air intraining agents for concrete or cement, additives to asphalt compositions, plasticizers and modifiers for vinyl plastics, alkyd resins and other types of polymeric-type plastic materials such as polythene, tefion, etc.; for incorporation into adhesives, paint, linoleum; into bonding agents used in various insulating and building materials; as refining aids in sulfite wood digesters to prepare pulp; as additives to pulp slurries in beating operations to prevent foaming and also to aid the beating operation in paper-making.

The invention may be illustrated by the following examples, although it is to be understood that the invention is not restricted thereto.

Example 1 A mixture of 2230 g. (24 mols) of dry toluene and 80 cc. of octene-l was stirred in a 5-liter, 3 necked flask equipped with a thermometer and dropping funnel. To this solution was added, at to C., 32 g. of powdered anhydrous aluminum chloride and 19 g. of dry hydrogen chloride gas. Octene-l was then added to the stirred mixture at 25 to 30 C. over a period of 1 hour, until a total of 860 cc. had been added (excluding the 80 cc. already present). The mixture was stirred for 3 hours at 25 to 30 C. and allowed to separate into layers. The lower layer containing aluminum chloride was separated and the upper layer washed first with a solution of 800 cc. of water and 160 cc. of concentrated hydrochloric acid, twice with solutions of 800 cc. of water and 160 cc. of sodium hydroxide and twice with 800 cc. of water. The toluene and water were removed by distillation. The residue of crude octyltoiuene was fractionated through a 12" helicesfilled column 1 in diameter. Final product boiled at 133 to 144 C. at 14 to 15 /2 millimeters pressure.

To 420 g. of chlorosulfonic acid stirred in a l-liter, 4-

necked flask to 5 to 10 C. was added 245 g. of octyitoluene over a period of 1% hours. The mixture was stirred for 3 hours at 25 to 30 C., allowed to stand overnight and then stirred into 900 g. of crushed ice.

The sulfonyl chloride was extracted with 500 cc. of ether and the ether layer washed with 400 cc. of cold water, twice with 400 cc. of cold water plus 50 cc. of 30% sodium carbonate and once with 400 cc. of cold water. The ether solution was dried over calcium chloride and the ether removed by distillation under reduced pressure. The residue was distilled under reduced pressure through a stillhead. There was obtained octyltoluenesulfonyl chloride boiling at 144 to 174 C. at 1 millimeter pressure.

In a 1-liter, 3-necked flask equipped with a stirrer and thermometer there was placed 86.5 g. (0.286 mol.) of octyltoluenesulfonyl chloride, 98 cc. of ethylene dichloride, and 134 g. (0.306 mol.) of 36.8% sodium methyl taurate solution. The mixture was stirred rapidly at C. and 63 cc. of 3.92 N NaOH was added in ten minutes holding the temperature between 45 and C. At one point the temperature rose to C. The mixture was stirred /2 hour at 45 C. The pH of four drops of the mixture in 20 cc. of water was 9.2. An additional 3.5 cc. of 3.92 N NaOH (total NaOH=0.289 mol.) was required to bring the pH up to 9.5 during an additional three hour stirring period at 30 C.

' The mixture was neutralized to pH 7.5 with 12.5 cc. (0.372 mol.) of 2.98 N HCl. A total of 55 cc. of solvent was removed by distilling to a pot temperature of 80 C. When the foaming became bad, 200 cc. of toluene was added. The water (234 cc.) was removed byfla moisture trap when the mixture was heated under re wt.

By filtering the toluene solution, 18.7 g. of dry salt was collected. Analysis showed that it contained 96.5% NaCl and no sulfur. The yield of sodium chloride from 0.286 mol. of octyltoluenesulfonyl chloride and 0.037 mol. of HCl would be 18.9 g. The toluene was distilled off under reduced pressure. The dry residue weighed 130.1 g.

A potentiometric titration showed that this residue contained 4.69 g. (0.034 mol.) of unreacted methyl taurine. Assuming that the remainder was converted to the desired product, there would be 116.4 g. (0.272 mol.) of sodium N-octyltoluenesulfonyl-N-methyltaurate in the residue corresponding to a yield of based on the acid chloride. The residue above would also contain 4.3 g. (0.014 mol.) of sodium octyltoluene sulfonate formed from the remainder of the sulfonyl chloride. Assuming that the remaining 4.7 g. of the residue represents 0.032 mol. of isethionic acid which is present as an impurity in the methyl taurine solution, the following values were obtained.

Calculated: S, 15.30, Na2SO4 ash, 17.35.

Found: S, 15.66, 15.37, Na2S04 ash, 17.13, 17.33.

The sodium N-octyltoluenesulfonyl-Nmethyltaurate prepared above was slightly inferior to Igepon T as a cotton detergent.

Example 2 i The procedure of Example 1 was repeated using 90.8 g. (0.3 mol.) octyltoluenesulfonyl chloride, 98 cc. ethylene dichloride and 390.4 g. (0.321 mol.) of 18.8% sodium cyclohexyltaurate.

The reaction was carried out at 5560 C., and a total of 0.412 mol. of 3.92 N NaOH was needed to keep the pH up to 9.5. The mixture was neutralized to pH 7.25 with 40.3 cc. of 2.98 N HCl. A brittle glassy residue weighing 151 g. was obtained by removing the toluene and drying. The yield of sodium N-octyltoluenesulfonyl- N-cyclehexyltaurate was 109 g. (73.3% of the theoretical 149 g.) based on a titration of the unreacted cyclohexyl taurine.

Example 3 Dodecyltoluene was prepared in the same way as the octyltoluene in Example 1, while utilizing the following quantity of reactants: 2230 g. (2550 cc.) of dry toluene, 885 cc. (672 g.) of dodecene-l, 21.5 g. of powdered anhydrous aluminum chloride and 22 g. of dry hydrogen chloride gas.

The dodecyltoluene obtained boiled at 177 to C. at 14 to 15 millimeters pressure.

To a stirred solution of 166 g. of dodecyltoluene in 400 cc. of dry chloroform, there was added dropwise in 67 minutes, 128 cc. of chlorosulfonic acid while maintaining the temperature at zero to 5 C. The mixture was stirred for 3 hours at 25 to 30 C., allowed to stand overnight and then poured into 450 g. of cracked ice.

The mixture stratified into layers and the chloroform layer was separated and washed with 500 cc. of ice water containing 50 cc. of a 30% salt solution; then twice with 500 cc. of ice water plus 50 cc. of 30% sodium carbonate soiution. Finally, with 500 cc. of ice water containing 50 cc. of a 30% salt solution.

The water layers were all extracted in succession with 400 cc. of ether and the ether and chloroform layers were dried over calcium chloride, the solvents being removed under reduced pressure while heating on a steam bath. The residue was distilled under reduced pressure to obtain dodecyltoluenesulfonyl chloride boiling at 193 to 220 C. at 2 to 2.7 millimeters.

The dodecyltoluenesulfonyl chloride was then converted to the taurate by following the procedure of Example 1 and whiie using the following quantities of reactants: 101 g. of crude dodecyltoluenesulfonyl chloride, 108 g. of ethylene dichloride, 134 g. of 36.8% of sodium methyl taurate and 92 cc. of 3.94 N sodium hydroxide.

During the reaction, 250 cc. of water was added to make the reaction mixture more fluid. The reaction mixture was heated at 55 to 60 C. during the final stirring period and was then neutralized to pH 6.9 with 21 cc. of 2.98 N HCl. The weight of dry solid residue was 135.2 g., containing 7.3 g. of unreacted methyl taurine. The yield of sodium N-dodecyltoluenesulfonyl-N-methyl taurate calculated from taurine used was 122.7 g., corresponding to a 90.5% yield based on 0.28 mol of the sulfonyl chloride.

Example 4 In a 1-liter, 4-necked flask equipped with a stirrer and thermometer was placed 105 cc. (124.8 g., 0.301 mol.) of 49% sodium butyltaurate and .100 cc. of distilled water. The solution was stirred at 45-50 C1, and there was added simultaneously from two burettes, 95.9 g. (approx. 0.27 mol.) of crude dodecyltoluenesulfonyl chloride and 71 cc. (0.28 mol.) of 3.94 N NaOH over a period of minutes. The temperature was held at 4550 C. for the first half of the addition, and at 55-60 C. for the last half. Stirring was continued for one hour.

A total of 71 cc. of 3.94 N NaOH was used to keep the pH to 9.5. The reaction mixture when diluted with 100 cc. water. and neutralized to pH 7.5 with 27 cc. 2.98 N HCl, weighed 532.7 g. Titration showed 0.085 mol. unused butyltaurine. The amount of reacted butyltaurine corresponded to 113.5 g. of sodium N-dodecyltoluenesulfonyl-N-butyltaurate. This is an 80% yield based on 0.27 mol. of sulfonyl chloride.

Example 5 The procedure of Example 1 was followed, using 114 g. (approx. 0.36 mol.) of crude diamylbenzenesulfonyl chloride, 162 g. ethylene dichloride, 175 g. (0.4 mol.) of 36.8% sodium methyltaurate, and 122 cc. (0.478 mol.) of 3.92 N NaOH. A dry solid residue was obtained which weighed 177.7 g. Analysis showed 7.1 g. of unreacted methyltaurine. The reacted methyltaurine corresponded to a yield of 154 g. (0.349 mol.) of sodium N- diamylbenzenesulfonyl-N-methyltaurate.

The diamylbenzenesulfonyl chloride was prepared in the same manner as the dodecyltoluenesulfonyl chloride while using 218 g. of diamylbenzene, 400 cc. of dry chloroform and 200 cc. of chlorosulfonic acid. The diamylbenzenesulfonyl chloride obtained boiled at 151 to 180 C. at 2 to 3 millimeters pressure.

Example 6 Using the following charge-186.3 g. of ethylene dichloride solution containing approx. 0.28 mol. of crude diamylbenzenesulfonyl chloride, 108 cc. (128.5 g.) of 49% sodium N-n-butyltaurate, and 93 cc. of 3.94 N Naoh, the procedure of Example 4 was repeated except that the addition of the sulfonyl chloride solution was started first, and the sodium hydroxide was added at such a rate that the pH remained between 9.3 and 9.9. The solvent was removed by distillation, leaving a solution weighing 653.2 g. Potentiometric titration showed that the solution contained 2.4% or 15.66 g. butyltaurine. The reacted butyltaurine corresponded to 108.2 g. (0.224 mol.) of sodium N diamylbenzenesulfonyl N butyltaurate.

Example 7 In a 1.5-liter stainless steel beaker equipped with a thermometer, baffies, and anchor type stirrer was placed 63.3 g. (0.2 mol.) of diamybenzenesulfonyl chloride, B. P. 152-164/1.3-2.3 mm., 163 g. (0.236 mol.) of 29.3% sodium N-(mixed) amylturate, and 160 cc. of distilled water.

The mixture was stirred at 45-50 C. and 63.5 cc. of 3.94 N NaOH was added dropwise bringing the pH to 9.75 at the end. The mixture was neutralized to pH 7.2 with 19.5 cc. of 4.017 N HCl. The clear solution weighed 485.5 g., and contained 15.5 g. or 3.2% amyltaurine. Based on reacted amyltaurine, the solution contained 77.8 g. or 16% by weight of sodium N-diamylbenzenesulfonyl-N-amyltaurate.

Example 8 The procedure of Example 7 was repeated using the following: 63.3 g. (0.2 mol.) of diamylbenzenesulfonyl chloride, B. P. 152-164/1.32.3 mm., 91.3 g. (0.22 mol.) of 49% N-n-butyltaurate, cc. distilled water, 57.1 cc. (0.225 mol.) of 3.94 N NaOH, 12.5 cc. (0.05 mol.) 4.017 N HCl.

The weight of neutral solution containing the product was 235.2 g. Analysis showed 13.2 g. of unreacted butyltaurate. From this a yield of 71.0 g. of sodium N- diamylbenzenesulfonyl-N-n-butyltaura'te was calculated.

Modifications of the invention will occur to persons skilled in the art. Thus as is evident, sulfonyl chlorides derived from any of the alkylbenzenes previously referred to may be reacted with any of the taurines previously mentioned to produce alternates of the specific products given in the examples.

We, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.

We claim:

1. Surface active agents having the following constitution wherein R1 is selected from the class consisting of alkyl group containing from 5 to 18 carbon atoms and cyclohexyl, R2 is selected from the class consisting of hydrogen and lower alkyl, the total number of carbon atoms in R1 and R2 being between 6 and 25, Ra is selected from the class consisting of alkyl group having from 1 to 12 carbon atoms, cyclohexyl andphenyl group, and M is a salt forming group.

2. Sodium N-diamylbenzenesulfonyl-N-n-butyl taurate.

3. Sodium N-diamylbenzenesulfonyl-N-amyl taurate.

4. Sodium N octyltoluenesulfonyl N cyclohexyl taurate.

5. Sodium N dodecylbenzenesulfonyl N methyl taurate.

6. Sodium N nonylbenzenesulfonyl N methyl taurate.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 648,568 Koetschet May 1, 1900 2,225,960 Orthner et al. Dec. 24, 1940 2,242,086 Platz et a1. May13, 1941 2,398,990 Albrecht Apr. 23, 1946 V UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,694,727 November 16, 1954 James M. Cross et al.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 80, for "(0.372 mol.)" read --(0.03'72 mol.)--.

Signed and sealed this 15th day of March, 1955.

(SEAL) Attest:

E, J, MURRY ROBERT C. WATSON Attesting Officer Commissioner of Patents 

1. SURFACE ACTIVE AGENTS HAVING THE FOLLOWING CONSTITUTION 